High voltage and high specific capacity dual intercalating electrode Li-ion batteries

Abstract

The present invention provides high capacity and high voltage Li-ion batteries that have a carbonaceous cathode and a nonaqueous electrolyte solution comprising LiF salt and an anion receptor that binds the fluoride ion. The batteries can comprise dual intercalating electrode Li ion batteries. Methods of the present invention use a cathode and electrode pair, wherein each of the electrodes reversibly intercalate ions provided by a LiF salt to make a high voltage and high specific capacity dual intercalating electrode Li-ion battery. The present methods and systems provide high-capacity batteries particularly useful in powering devices where minimizing battery mass is important.

1. An electrochemical cell comprising:
 a. opposed anode and cathode electrodes, wherein said cathode electrode comprises a carbonaceous material and said opposed electrodes are dual ion-intercalating electrodes; and 
 b. a nonaqueous electrolyte solution in ionic contact with said cathode and said anode, wherein said electrolyte solution comprises LiF and an anion receptor; 
 c. wherein said anion receptor in contact with said electrolyte such that said anion receptor increases the conductivity of the nonaqueous electrolyte solution by binding a fluoride anion of said LiF to provide intercalation of Li +  ions at the anode and F −  ions at the cathode during charge. 
 
     
     
       2. The electrochemical cell of  claim 1  wherein said carbonaceous material comprises a carbonaceous layer on a metal foil. 
     
     
       3. The electrochemical cell of  claim 2  wherein said carbonaceous material is graphite, coke or carbon polymonofluoride. 
     
     
       4. The electrochemical cell of  claim 1  wherein said anode comprises lithium metal or lithium metal alloy. 
     
     
       5. The electrochemical cell of  claim 1  wherein said anode comprises a carbonaceous material. 
     
     
       6. The electrochemical cell of  claim 1  wherein said nonaqueous electrolyte further comprises a propylene carbonate solvent. 
     
     
       7. The electrochemical cell of  claim 1  wherein said anion receptor has the formula 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  are independently selected from the group consisting of alkyl, aromatic, ether, thioether, heterocyclic, aryl or heteroaryl groups which are optionally substituted with one or more halogens, including F, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether. 
       
     
     
       8. The electrochemical cell of  claim 7 , wherein said anion receptor has the formula: 
       
         
           
           
               
               
           
         
       
     
     
       9. The electrochemical cell of  claim 7 , wherein said anion receptor has the formula: 
       
         
           
           
               
               
           
         
       
     
     
       10. The electrochemical cell of  claim 7 , wherein said anion receptor has the formula: 
       
         
           
           
               
               
           
         
       
     
     
       11. The electrochemical cell of  claim 1  wherein said anion receptor is selected from the group consisting of aza-ether based compounds, fluorinated boron-based compounds, and phenyl boron-based compounds. 
     
     
       12. The electrochemical cell of  claim 1  wherein said electrochemical cell has an operating cell voltage greater than or equal to 5 V. 
     
     
       13. The electrochemical cell of  claim 1  wherein said electrochemical cell has a cathode specific capacity greater than or equal to 400 Whr/kg. 
     
     
       14. A dual intercalating electrode Li-ion battery comprising:
 a. opposed anode and cathode electrodes, wherein each of said anode and cathode electrode comprise a carbonaceous material capable of reversibly intercalating an ion; 
 b. a nonaqueous electrolyte in ionic contact with each of said electrodes, wherein said electrolyte comprises LiF; and 
 c. an anion receptor in contact with said electrolyte such that said anion increases the conductivity of the nonaqueous electrolyte solution by binding fluoride anion; 
 
       wherein said anode reversibly intercalates Li +  ions and said cathode reversibly intercalates F −  ions during charge. 
     
     
       15. The battery of  claim 14  wherein the carbonaceous material comprises a carbonaceous layer on a metal foil. 
     
     
       16. The battery of  claim 14  wherein at least one of the carbonaceous anode material and carbonaceous cathode material is graphite, coke or carbon polymonofluoride. 
     
     
       17. The battery of  claim 14  wherein the electrolyte further comprises a propylene carbonate solvent. 
     
     
       18. The battery of  claim 14  wherein the LiF has a molarity range between about 1M and 5M. 
     
     
       19. The battery of  claim 14  wherein said anion receptor has the formula 
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2  and R 3  are independently selected from the group consisting of alkyl, aromatic, ether, thioether, heterocyclic, aryl or heteroaryl groups which are optionally substituted with one or more halogens, including F, alkyl, alkoxide, thiol, thioalkoxide, aromatic, ether or thioether. 
     
     
       20. The battery of  claim 14 , wherein said anion receptor has the formula: 
       
         
           
           
               
               
           
         
       
     
     
       21. The battery of  claim 19 , wherein said anion receptor has the formula: 
       
         
           
           
               
               
           
         
       
     
     
       22. The battery of  claim 14 , wherein said anion receptor is selected from the group consisting of aza-ether based compounds, fluorinated boron-based compounds, and phenyl boron-based compounds. 
     
     
       23. The battery of  claim 14  wherein said electrochemical cell has an operating cell voltage greater than or equal to 5 V. 
     
     
       24. The battery of  claim 14  wherein said electrochemical cell has a cathode specific capacity greater than or equal to 400 Whr/kg. 
     
     
       25. A method of making a dual intercalating ion electrode lithium-ion battery comprising:
 a. providing a cathode and an anode in an opposed configuration, wherein the cathode and the anion reversibly intercalate ions; 
 b. providing a nonaqueous electrolyte solution in ionic contact with each of the cathode and the anode, wherein the electrolyte solution comprises LiF and an anion receptor to increase the conductivity of the nonaqueous electrolyte solution by binding a fluoride ion of said LiF; and 
 c. supplying an electrical potential difference between the cathode and the anode such that the fluoride ion intercalates with the cathode and a lithium ion of said LiF intercalates with the anode, 
 
       thereby making a dual intercalating ion electrode lithium-ion battery. 
     
     
       26. The method of  claim 25  further comprising discharging the battery by reversing the electrical potential such that fluoride ions deintercalate from the cathode and lithium ions deintercalate from the anode. 
     
     
       27. The battery of  claim 14 , wherein said cathode carbonaceous material is graphite, petroleum coke or amorphous carbon. 
     
     
       28. The electrochemical cell of  claim 1  wherein said cathode carbonaceous material is graphite, petroleum coke or amorphous carbon.